Glass for medicine container and glass tube for medicine container

ABSTRACT

The present invention relates to a glass for a pharmaceutical container that is excellent in ultraviolet shielding ability, and is also excellent in chemical durability. The glass for a pharmaceutical container of the present invention includes as a glass composition, in terms of mass %, 67% to 81% of SiO2, more than 4% to 7% of Al2O3, 7% to 14% of B2O3, 3% to 12% of Na2O+K2O, 0% to 1.8% of CaO+BaO, 0.5% to less than 2% of Fe2O3, and 1% to 5% of TiO2, and satisfies a relationship of CaO/BaO≤0.5.

TECHNICAL FIELD

The present invention relates to a glass for a pharmaceutical containerand a glass tube for a pharmaceutical container that are each excellentin ultraviolet shielding ability, and are each also excellent inchemical durability.

BACKGROUND ART

Various glasses have hitherto been used as materials for containers tobe filled for storing pharmaceuticals. While the pharmaceuticals areroughly divided into two kinds: an oral drug and a parenteral drug, inparticular, the parenteral drug is directly administered to blood of apatient as a drug solution filled and stored in a glass container, andhence the glass container is required to have significantly highquality. Pharmaceutical containers have two kinds of color tones:colorless and colored. Out of such pharmaceutical containers, thecolored container is required to have a function of blocking ultravioletlight so that a pharmaceutical included therein is not altered throughirradiation with light. For example, in the case of a drug containingVitamin C, Vitamin C may be altered with ultraviolet light. As a methodof solving such problem, there has been developed a glass for apharmaceutical container in which the glass is colored to have afunction of blocking ultraviolet light (for example, see PatentLiteratures 1 and 2). In addition, in pharmacopoeias of variouscountries, with regard to a colored glass for a pharmaceuticalcontainer, an upper limit of a transmittance within a specificwavelength range is specified.

In addition, the pharmaceutical container is required not to altercomponents of a drug solution filled therein owing to an eluted materialfrom the container. When glass components are eluted into the drugsolution, there is a risk in that the properties of the drug solutionare altered, which affects the health of a patient and even the life ofthe patient. Therefore, in the pharmacopoeias of various countries, theelution amounts of the glass components of the glass for apharmaceutical container are specified.

In general, a borosilicate glass is used as the glass for apharmaceutical container. Moreover, a colored borosilicate glass for apharmaceutical container having a function of blocking ultraviolet lightincludes, as a glass composition, SiO₂, Al₂O₃, B₂O₃, Na₂O, K₂O, CaO,BaO, Fe₂O₃, TiO₂, and a small amount of a fining agent.

Incidentally, in recent years, many kinds of new drugs have been createdthrough rapid advances in pharmacology, and also a drug to be filled inthe pharmaceutical container has been changed. A relatively inexpensivedrug, such as a blood coagulant or an anesthetic drug, has hitherto beenmainly filled therein, but recently, a prophylactic agent, such as aninfluenza vaccine, or a significantly expensive drug, such as ananticancer drug, has been often filled therein. Along with this, theborosilicate glass for a pharmaceutical container, which forms a vial oran ampoule, is required to have higher chemical durability (hydrolyticresistance, alkali resistance, acid resistance, and the like) than everbefore. Moreover, the colored borosilicate glass for a pharmaceuticalcontainer may also be similarly required to have such high chemicaldurability.

In Patent Literature 1, there is disclosed an amber coloredpharmaceutical glass having the above-mentioned components. However, itis hard to say that such glass satisfies the chemical durabilityrequired in recent years.

In addition, in Patent Literature 2, there is described that, in a glasshaving high chemical durability, for example, the content of an alkalimetal oxide, such as Li₂O, Na₂O, or K₂O, or an alkaline earth metaloxide, such as MgO, CaO, SrO, or BaO, contained in the glass is reduced,or the content of Al₂O₃ contained therein is increased. However, it isinsufficient to merely increase or reduce the content of each componentfor satisfying the chemical durability required in recent years.

CITATION LIST

-   Patent Literature 1: JP 38-5014 B-   Patent Literature 2: JP 2608535 B2

SUMMARY OF INVENTION Technical Problem

The present invention has been made in view of the above-mentionedcircumstances, and the present invention provides a colored glass for apharmaceutical container and a colored glass tube for a pharmaceuticalcontainer that are each excellent in ultraviolet shielding ability, andare each also excellent in chemical durability.

Solution to Problem

The inventor of the present invention has made various investigations,and as a result, has found that the above-mentioned problems can besolved by optimizing the contents of alkaline earth metal oxides,specifically by strictly controlling the total content of CaO and BaOserving as the alkaline earth metal oxides, and the ratio between CaOand BaO. Thus, the finding is proposed as the present invention.

That is, according to one embodiment of the present invention, there isprovided a glass for a pharmaceutical container, which comprises as aglass composition, in terms of mass %, 67% to 81% of SiO₂, more than 4%to 7% of Al₂O₃, 7% to 14% of B₂O₃, 3% to 12% of Na₂O+K₂O, 0% to 1.8% ofCaO+BaO, 0.5% to less than 2% of Fe₂O₃, and 1% to 5% of TiO₂, andsatisfies a relationship of CaO/BaO≤0.5.

Here, the “Na₂O+K₂O” means the total of the contents of Na₂O and K₂O.The “CaO+BaO” means the total of the contents of CaO and BaO. The“CaO/BaO≤0.5” means that a value obtained by dividing the content of CaOby the content of BaO is 0.5 or less.

The glass for a pharmaceutical container according to the one embodimentof the present invention is colored in reddish-brown, that is, ambercolored by virtue of Fe₂O₃ and TiO₂, and is thus excellent inultraviolet shielding ability.

Further, the values for CaO+BaO and CaO/BaO are controlled as describedabove, and hence the elution of CaO and BaO from the glass is reduced.Thus, more excellent chemical durability, in particular, hydrolyticresistance can be obtained.

Besides, the value for Na₂O+K₂O is controlled as described above, andhence the glass for a pharmaceutical container according to the oneembodiment of the present invention is easily processed into acontainer, such as an ampoule or a vial. Accordingly, both satisfactoryhydrolytic resistance required for a pharmaceutical container and easyprocessability into a container, such as an ampoule or a vial, can beachieved.

In addition, it is preferred that the glass for a pharmaceuticalcontainer according to the one embodiment of the present inventioncomprise as a glass composition, in terms of mass %, 70% to 78% of SiO₂,5% to 7% of Al₂O₃, 8% to 11% of B₂O₃, 6% to 10% of Na₂O+K₂O, 0% to 1.8%of CaO+BaO, 0.8% to 1.2% of Fe₂O₃, and 2% to 5% of TiO₂, and satisfy arelationship of CaO/BaO≤0.3.

With this, the glass for a pharmaceutical container that is colored in adesired color and exhibits more excellent chemical durability can beeasily obtained.

It is preferred that the glass for a pharmaceutical container accordingto the one embodiment of the present invention comprise, as a glasscomposition, in terms of mass %, 9% to 11% of B₂O₃.

With this, the glass that has more satisfactory processability into acontainer can be obtained.

It is preferred that the glass for a pharmaceutical container accordingto the one embodiment of the present invention comprise, as a glasscomposition, in terms of mass %, 0% to 1% of CaO and 0.1% to 2% of BaO.

With this, the glass that has excellent hydrolytic resistance preferredfor applications as a pharmaceutical container can be obtained.

It is preferred that the glass for a pharmaceutical container accordingto the one embodiment of the present invention have a consumption amountof 0.02 mol/L hydrochloric acid per unit glass mass of 0.035 mL or lessin a hydrolytic resistance test by a glass grains test method inconformity with the European Pharmacopoeia 7.0. The “hydrolyticresistance in the test in conformity with the European Pharmacopoeia7.0” as used herein refers to the degree of an alkali elution amountdetermined by the following method.

(1) A glass sample is crushed in an alumina mortar and classified into aparticle diameter of from 300 μm to 425 μm with a sieve.

(2) The resultant powder sample is washed with distilled water andethanol and dried in an oven at 140° C.

(3) 10 g of the powder sample after the drying is loaded into a quartzflask, and 50 mL of distilled water is further added thereto and theflask is covered with a closure, followed by treatment in an autoclave.The treatment is performed under the following treatment conditions: atemperature is increased at a rate of 1° C./min from 100° C. to 121° C.,and is then retained at 121° C. for 30 minutes, and is reduced at a rateof 0.5° C./min to 100° C.(4) After the treatment in an autoclave, the solution in the quartzflask is transferred to another beaker, the quartz flask is furtherwashed with 15 mL of distilled water, and also the washing liquid isadded to the beaker.(5) A methyl red indicator solution is added to the beaker, and thecontent is titrated with a 0.02 mol/L hydrochloric acid solution.(6) The consumption amount of hydrochloric acid required forneutralization is converted to the consumption amount of hydrochloricacid per gram of glass.

In addition, the “having hydrolytic resistance of at least Type I in thetest in conformity with the European Pharmacopoeia 7.0” means that theconsumption amount of hydrochloric acid determined by theabove-mentioned test is 0.1 ml/g or less.

It is preferred that the glass for a pharmaceutical container accordingto the one embodiment of the present invention have a working point of1,200° C. or less. The “working point” as used herein means atemperature at which the glass has a viscosity of 10⁴ dPa·s.

According to the above-mentioned configuration, a processing temperatureat the time of manufacturing a glass container, such as an ampoule or avial, from a glass tube can be reduced, and hence the evaporation amountof an alkali component in the glass can be significantly reduced. As aresult, for example, a situation in which components of a drug solutionto be stored in the glass container are altered or the pH of the drugsolution is increased can be avoided.

It is preferred that the glass for a pharmaceutical container accordingto the one embodiment of the present invention have a transmittance at awavelength of 450 nm of 15% or less when having a thickness of 1 mm.

According to one embodiment of the present invention, there is provideda glass for a container, which comprises as a glass composition, interms of mass %, 67% to 81% of SiO₂, more than 4% to 7% of Al₂O₃, 7% to14% of B₂O₃, 3% to 12% of Na₂O+K₂O, 0% to 1.8% of CaO+BaO, 0.5% to lessthan 2% of Fe₂O₃, and 1% to 5% of TiO₂, and satisfies a relationship ofCaO/BaO≤0.5.

According to one embodiment of the present invention, there is provideda glass tube for a pharmaceutical container, comprising theabove-mentioned glass for a pharmaceutical container.

According to one embodiment of the present invention, there is providedglass tube for a container, comprising the above-mentioned glass for acontainer.

DESCRIPTION OF EMBODIMENTS

The reasons why the composition ranges of components are limited aredescribed. In the following description, the expression “%” means “mass%” unless otherwise specified.

SiO₂ is one of components that forma network structure of a glass. Whenthe content of SiO₂ is too large, it becomes difficult to achieve aworking point of 1,200° C. or less. When the content of SiO₂ is toosmall, it becomes difficult to vitrify the glass. In addition, the glassis increased in thermal expansion coefficient, and is thus liable to bereduced in thermal shock resistance. Therefore, the content thereof ispreferably 65% or more, 67% or more, 69% or more, or 70% or more,particularly preferably 71% or more, and is preferably 81% or less, 78%or less, 76% or less, or 75% or less, particularly preferably 73% orless. For example, the range of SiO₂ is desirably from 67% to 73%,particularly desirably from 70% to 73%.

Al₂O₃ is one of the components that form the network structure of theglass, and has an effect of improving the hydrolytic resistance of theglass. Therefore, the content thereof is preferably 3% or more, 4% ormore, or more than 4%, particularly preferably 5% or more, and ispreferably 10% or less, 9% or less, 8% or less, 7% or less, or 6% orless. The range of Al₂O₃ is desirably from more than 4% to 7%,particularly desirably from 5% to 7%. When the content of Al₂O₃ is toosmall, it becomes difficult to achieve the requirements of hydrolyticresistance of Type I in a test in conformity with the EuropeanPharmacopoeia 7.0. Meanwhile, when the content of Al₂O₃ is too large, itbecomes difficult to achieve a working point of 1,200° C. or less.

B₂O₃ has an effect of reducing the viscosity of the glass. When thecontent of B₂O₃ is too large, the chemical durability of the glass isreduced. When the content of B₂O₃ is too small, it becomes difficult toachieve a working point of 1,200° C. or less. Therefore, the contentthereof is preferably 5% or more, 6% or more, 7% or more, or 8% or more,particularly preferably 9% or more, and is preferably 16% or less, 15%or less, 14% or less, 13% or less, or 12% or less, particularlypreferably 11% or less. The content of B₂O₃ is desirably from 7% to 14%,particularly desirably from 8% to 11%.

Li₂O, Na₂O, and K₂O serving as alkali metal oxides (R₂O) each have aneffect of reducing the viscosity of the glass. However, when the totalcontent of those components is large, an alkali elution amount from theglass is increased. Further, the thermal expansion coefficient isincreased, and thus the thermal shock resistance is reduced. When thecontent of the alkali metal oxides is too small, it becomes difficult toachieve a working point of 1,200° C. or less. Therefore, the totalcontent of R₂O is preferably from 3% to 12%, from 4% to 10%, from 5% to9%, or from 6% to 8%, particularly preferably from 7% to 8%.

As described above, Li₂O has an effect of reducing the viscosity of theglass to increase the processability and the meltability of the glass.When the content of Li₂O is too large, the alkali elution amount fromthe glass is increased. Further, the thermal expansion coefficient isincreased, and thus the thermal shock resistance is reduced. When thecontent of Li₂O is too small, it becomes difficult to achieve a workingpoint of 1,200° C. or less. However, a raw material of Li₂O is moreexpensive than those of other alkali metal oxides, which results in anincrease in manufacturing cost. Therefore, the content of Li₂O ispreferably from 0% to 1%, particularly preferably from 0% to 0.5%.

Na₂O is a component that reduces the viscosity of the glass as withLi₂O. When the content of Na₂O is too large, the alkali elution amountfrom the glass is increased. Further, the thermal expansion coefficientis increased, and thus the thermal shock resistance is reduced. When thecontent of Na₂O is too small, it becomes difficult to achieve a workingpoint of 1,200° C. or less. Therefore, the content of Na₂O is preferablyfrom 0% to 12%, from 1% to 10%, from 3% to 8%, or from 4% to 7%,particularly preferably from 5% to 6%.

K₂O is a component that reduces the viscosity of the glass as with Li₂Oand Na₂O. When the content of K₂O is too large, the alkali elutionamount from the glass is increased. Further, the thermal expansioncoefficient is increased, and thus the thermal shock resistance isreduced. When the content of K₂O is too small, it becomes difficult toachieve a working point of 1,200° C. or less. Therefore, the content ofK₂O is preferably from 0% to 12%, from 1% to 10%, from 1.2% to 7%, from1.5% to 5%, or from 1.6% to 3%, particularly preferably from 2% to 3%.

As a result of investigations made from the two viewpoints of thecharacteristics of the glass and the manufacturing cost thereof, it ispreferred that two components of Na₂O and K₂O coexist as alkali metaloxides contained in the glass. However, when the content of Na₂O+K₂O istoo large, the alkali elution amount from the glass is increased.Further, the thermal expansion coefficient is increased, and thus thethermal shock resistance is reduced. When the content of Na₂O+K₂O is toosmall, it becomes difficult to achieve a working point of 1,200° C. orless. Therefore, the content of Na₂O+K₂O is preferably 3% or more, 4% ormore, 5% or more, or 6% or more, particularly preferably 7% or more, andis preferably 12% or less, 10% or less, or 9% or less, particularlypreferably 8% or less. The content of Na₂O+K₂O is desirably from 3% to12%, from 3% to 9%, or from 6% to 10%, particularly desirably from 6% to9%.

MgO, CaO, SrO, and BaO serving as alkaline earth metal oxides (R′O) eachhave an effect of reducing the viscosity of the glass. In addition, MgO,CaO, SrO, and BaO each also affect the alkali elution amount. When thecontent of the alkaline earth metal oxides is too large, the alkalielution amount from the glass is increased. Further, the thermalexpansion coefficient is increased, and thus the thermal shockresistance is reduced. When the content of the alkaline earth metaloxides is too small, it becomes difficult to achieve a working point of1,200° C. or less. Accordingly, the total content of the alkaline earthmetal oxides is preferably from 0% to 5%, from 0.1% to 4%, from 0.3% to3%, or from 0.5% to 2%, particularly preferably from 0.9% to 1.8%.

MgO has an effect of reducing the viscosity of the glass. In addition,MgO also affects the alkali elution amount. When the content of MgO istoo large, the alkali elution amount from the glass is increased.Further, the thermal expansion coefficient is increased, and thus thethermal shock resistance is reduced. Therefore, the content of MgO ispreferably from 0% to 4%, from 0% to 1%, or from 0% to 0.7%,particularly preferably from 0% to 0.4%.

CaO has an effect of reducing the viscosity of the glass. In addition,CaO also affects the alkali elution amount. When the content of CaO istoo large, the alkali elution amount from the glass is increased.Further, the thermal expansion coefficient is increased, and thus thethermal shock resistance is reduced. Therefore, the content of CaO ispreferably from 0% to 4%, from 0% to 1%, or from 0% to 0.7%,particularly preferably from 0% to 0.4%. A raw material of CaO isavailable more inexpensively than those of other alkaline earth metaloxides, and hence the manufacturing cost can be reduced.

SrO has an effect of reducing the viscosity of the glass. In addition,SrO also affects the alkali elution amount. When the content of SrO istoo large, the alkali elution amount from the glass is increased.Further, the thermal expansion coefficient is increased, and thus thethermal shock resistance is reduced. Therefore, the content of SrO ispreferably from 0% to 1%, particularly preferably from 0% to 0.5%.

BaO has an effect of reducing the viscosity of the glass. In addition,BaO also affects the alkali elution amount. When the content of BaO istoo large, the alkali elution amount from the glass is increased.Further, the thermal expansion coefficient is increased, and thus thethermal shock resistance is reduced. When the content of BaO is toosmall, it becomes difficult to achieve a working point of 1,200° C. orless. Therefore, the content of BaO is preferably from 0% to 5%, from 0%to 2%, or from 0.1% to 1.8%, particularly preferably from 0.6% to 1.5%.

The alkaline earth metal oxides each have an effect of improving thedevitrification resistance of the glass, and the magnitudes thereofbecome larger in the order of MgO<CaO<SrO<BaO. Accordingly, when BaO ispreferentially selected as the alkaline earth metal oxide, thedevitrification resistance of the glass can be improved mosteffectively. As a result, the productivity of the glass duringmanufacturing and processing of the glass can be improved.

In addition, when the contents of the alkaline earth metal oxides arethe same, these glass components are less liable to be eluted into adrug solution or the like in the order of MgO>CaO>SrO>BaO, that is, indescending order of the number of atoms contained in the glass.Accordingly, when BaO is selected, the elution of the glass componentcan be suppressed most effectively.

As a result of investigations made from the two viewpoints of thecharacteristics of the glass and the manufacturing cost thereof,preferred alkaline earth metal oxides to be contained in the glass areCaO and BaO. When the content of CaO+BaO is too large, the alkalielution amount from the glass is increased. Further, the thermalexpansion coefficient is increased, and thus the thermal shockresistance is reduced. When the content of CaO+BaO is too small, itbecomes difficult to achieve a working point of 1,200° C. or less.Therefore, the content thereof is preferably 0% or more, 0.1% or more,0.3% or more, or 0.5% or more, particularly preferably 0.9% or more, andis preferably 5% or less, 4% or less, 3% or less, or 2% or less,particularly preferably 1.8% or less. The content of CaO+BaO isdesirably from 0% to 1.8%.

In addition, the contents of CaO and BaO are preferably such that therelationship of CaO≤BaO is satisfied, and are more preferably such thatthe relationship of CaO<BaO is satisfied. Further, a particularlypreferred relationship between the contents of CaO and BaO is asfollows: CaO/BaO, that is, a value obtained by dividing the content ofCaO by the content of BaO is preferably from 0 to 0.5, from 0 to 0.45,from 0 to 0.37, from 0 to 0.3, or from 0 to 0.25, particularlypreferably from 0 to 0.1. When the CaO/BaO is too large, the hydrolyticresistance deteriorates. As the CaO/BaO becomes smaller, the glasshaving more excellent hydrolytic resistance can be obtained.

Fe₂O₃ is an essential component for coloring of the glass. When thecontent of Fe₂O₃ is too large, the elution amount of an Fe componentfrom the glass is increased. When the content of Fe₂O₃ is too small, anultraviolet shielding ability required for a pharmaceutical container isnot obtained. Therefore, the content of Fe₂O₃ is preferably 0.1% ormore, 0.6% or more, 0.8% or more, or 0.85% or more, particularlypreferably 0.9% or more, and is preferably 3% or less, 2% or less, 1.4%or less, or 1.2% or less, particularly preferably 1.1% or less. Thecontent of Fe₂O₃ is desirably from 0.5% to less than 2%, particularlydesirably from 0.8% to 1.2%.

TiO₂ is an essential component for coloring of the glass as with Fe₂O₃,and it is preferred that Fe₂O₃ and TiO₂ coexist in the glass in order toobtain the ultraviolet shielding ability of the present invention. Whenthe content of TiO₂ is too large, the elution amount of a Ti componentfrom the glass is increased. When the content of TiO₂ is too small, theultraviolet shielding ability required for a pharmaceutical container isnot obtained. Therefore, the content of TiO₂ is 0.1% or more, 1% ormore, 1.6% or more, or 2% or more, particularly preferably 2.1% or more,and is preferably 5% or less, 4.5% or less, 4.1% or less, or 3% or less,particularly preferably 2.6% or less. The content of TiO₂ is desirablyfrom 1% to 5%, particularly desirably from 2% to 5%.

The glass for a pharmaceutical container of the present invention maycomprise one or more kinds selected from, for example, F, Cl, Sb₂O₃,As₂O₃, SnO₂, and Na₂SO₄ as a fining agent. In this case, the standardcontent of the fining agent is, in terms of the total content, 5% orless, and is particularly preferably 1% or less, still more preferably0.5% or less.

In addition, the glass for a pharmaceutical container of the presentinvention may comprise any other component than those described above.For example, in order to improve the chemical durability, a viscosity athigh temperature, and the like, ZnO, P₂O₅, Cr₂O₃, PbO, La₂O₃, WO₃,Nb₂O₃, Y₂O₃, and the like may each be added up to 3%.

When the present invention is performed, a component that has an actionof reducing the iron component in the glass, such as carbon, metalaluminum, or metal sulfur, may be incorporated. While the content of areducing agent may be appropriately adjusted in view of thetransmittance or the molten state of the glass, the content of thereducing agent is, in terms of the total content, 5% or less, preferably1% or less, more preferably 0.5% or less, most preferably 0.1% or less.In addition, in order to adjust the degree of reduction, iron rawmaterials having different redox states, such as ferric oxide andtriiron tetraoxide, may be used.

In addition, components such as H₂, CO₂, CO, H₂O, He, Ne, Ar, and N₂ mayeach be incorporated up to 0.1% as an impurity. In addition, the amountsof noble metal elements mixed therein, such as Pt, Rh, and Au, are eachpreferably 500 ppm or less, more preferably 300 ppm or less.

The glass for a pharmaceutical container of the present invention has aconsumption amount of 0.02 mol/L hydrochloric acid per unit glass massof preferably 0.040 mL or less, less than 0.038 mL, or less than 0.035mL, particularly preferably 0.033 mL or less, most preferably 0.030 mLor less in a hydrolytic resistance test by a glass grains test method inconformity with the European Pharmacopoeia 7.0. When the consumptionamount of hydrochloric acid is more than 0.1 mL, there is a risk inthat, when a container, such as an ampoule or a vial, is produced, and adrug solution is filled and stored therein, the elution of the glasscomponents, in particular, an alkali component is significantlyincreased to cause alteration of components of the drug solution.

In addition, the glass for a pharmaceutical container of the presentinvention has a working point of preferably 1,250° C. or less, 1,230° C.or less, 1,200° C. or less, or 1,190° C. or less, particularlypreferably 1,180° C. or less. When the working point becomes higher, aprocessing temperature at the time of processing a glass tubing into anampoule or a vial also becomes higher, and the evaporation of the alkalicomponent contained in the glass is significantly increased. Theevaporated alkali component adheres to an inner wall of the glasstubing, and such glass tubing is processed into a glass container. Whena drug solution is filled and stored in such glass container, the glasscontainer causes alteration of the drug solution. In addition, when theglass has an excessively large content of a boron component, also theevaporation of boron occurs. The boron adheres to the inner wall of theglass tubing as with the alkali component, which results in theformation of an alteration layer having inferior hydrolytic resistanceto that in the case of having the original glass composition.

In addition, the glass for a pharmaceutical container of the presentinvention has a temperature at which the glass has a viscosity of10^(2.5) dPa·s of preferably 1,700° C. or less, more preferably 1,650°C. or less, most preferably 1,600° C. or less.

Incidentally, with regard to light shielding properties of a coloredpharmaceutical container, it is specified in the European Pharmacopoeiaor the United States Pharmacopeia that a light transmittance measured atwavelength intervals of 20 nm in a short-wavelength region (from 290 nmto 450 nm) is 50% or less. Therefore, the glass for a pharmaceuticalcontainer of the present invention has a light transmittance measured atwavelength intervals of 20 nm in the short-wavelength region (from 290nm to 450 nm) of preferably 50% or less, more preferably 40% or less,particularly preferably 30% or less. With this, the EuropeanPharmacopoeia or the United States Pharmacopeia is easily satisfied.

In particular, the glass for a pharmaceutical container of the presentinvention preferably has a transmittance at a wavelength of 450 nm of15% or less when having a thickness of 1 mm. With this, the glass thatsatisfies the European Pharmacopoeia or the United States Pharmacopeiacan be easily obtained.

As described above, the glass for a pharmaceutical container of thepresent invention is suitable for applications as a pharmaceuticalcontainer, but may be used as a glass for a container other than thepharmaceutical container by virtue of being excellent in hydrolyticresistance and light shielding properties.

A glass for a container of the present invention has a glass compositionin common with the glass composition of the glass for a pharmaceuticalcontainer of the present invention having been specifically described,and the description thereof is omitted.

Next, a manufacturing method for a glass tube for a pharmaceuticalcontainer of the present invention is described. The followingdescription is given of an example using a Danner method.

First, glass raw materials are blended so as to give the above-mentionedglass composition, to thereby produce a glass batch. Next, the glassbatch is continuously loaded into a melting kiln at from 1,550° C. to1,700° C. to be melted and fined, and then, while the resultant moltenglass is wound around an external surface of a rotating cylindricalrefractory, the molten glass is drawn from a tip of the refractory withblowing of air, to thereby form the glass into a tube shape from thetip.

While an example of the resultant tubular glass is not limited thereto,the tubular glass may have an outer diameter of from 1 mm to 100 mm,from 3 mm to 70 mm, or from 7 mm to 55 mm. In addition, for example, thetubular glass may have a thickness of from 0.1 mm to 10 mm, from 0.2 mmto 5 mm, or from 0.4 mm to 3 mm.

Subsequently, the tubular glass having been drawn is cut into apredetermined length. Thus, a glass tube for a pharmaceutical containeris obtained. The glass tube thus obtained is subjected to manufacturingof a vial or an ampoule.

As described above, the glass tube for a pharmaceutical container of thepresent invention is suitable for manufacturing of a pharmaceuticalcontainer, but may be subjected to manufacturing of a container otherthan the pharmaceutical container.

Without limitation to the Danner method, the glass tube for apharmaceutical container of the present invention may be manufactured byany method that has hitherto been well known. For example, a Vellomethod and a down-draw method are each useful as the manufacturingmethod for the glass tube for a pharmaceutical container of the presentinvention.

In addition, for a glass tube for a container of the present invention,the manufacturing method having been described for the glass tube for apharmaceutical container of the present invention may be appropriatelyadopted, and the description thereof is omitted.

EXAMPLES

The present invention is described below by way of Examples.

Examples (Sample Nos. 1 to 41 and 45 to 50) and Comparative Examples(Sample Nos. 42 to 44) of the present invention are shown in Tables 1 to5.

TABLE 1 Mass % No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 SiO₂ 72.17 71.7772.17 71.97 71.42 72.22 Al₂O₃ 5.40 5.40 5.40 5.40 5.70 5.40 B₂O₃ 9.509.50 9.50 9.50 9.50 9.50 CaO 0.40 0.40 0.40 0.40 0.40 BaO 1.30 1.30 1.301.30 1.20 1.30 Na₂O 5.1 5.50 5.75 5.30 5.70 5.45 K₂O 2.35 2.35 1.70 2.352.30 2.35 Cl 0.08 0.08 0.08 0.08 0.08 0.08 Fe₂O₃ 1.20 1.20 1.20 1.201.20 1.20 TiO₂ 2.50 2.50 2.50 2.50 2.50 2.50 SnO₂ Na₂O + K₂O 7.45 7.857.45 7.65 8.00 7.80 CaO + BaO 1.70 1.70 1.70 1.70 1.60 1.30 CaO/BaO 0.310.31 0.31 0.31 0.33 0.00 10^(2.5) dPa · s (° C.) 1,591 1,558 1,566 1,5751,563 Working point (10⁴ 1,180 1,156 1,160 1,168 1,158 dPa · s) (° C.)Hydrolytic 0.0290 0.0320 0.0325 0.0305 0.0330 resistance (ml/g) Linearthermal 51.9 53.4 expansion coefficient (from 30° C. to 380° C.)Transmittance at a 11 wavelength of 450 nm (thickness: 1 mm) (%) Mass %No. 7 No. 8 No. 9 No. 10 No. 11 SiO₂ 71.27 71.07 71.42 72.12 72.02 Al₂O₃5.90 5.90 5.90 5.40 5.40 B₂O₃ 9.50 9.50 9.50 9.50 9.50 CaO 0.40 0.400.40 0.20 BaO 0.80 0.80 0.80 1.30 1.30 Na₂O 5.45 5.65 5.55 5.40 5.70 K₂O2.90 2.90 2.65 2.35 2.35 Cl 0.08 0.08 0.08 0.08 0.08 Fe₂O₃ 1.20 1.201.20 1.15 1.15 TiO₂ 2.50 2.50 2.50 2.50 2.50 SnO₂ Na₂O + K₂O 8.35 8.558.20 7.75 8.05 CaO + BaO 1.20 1.20 1.20 1.50 1.30 CaO/BaO 0.50 0.50 0.500.15 0.00 10^(2.5) dPa · s (° C.) 1,568 1,561 1,574 1,579 1,562 Workingpoint (10⁴ 1,162 1,156 1,166 1,169 1,154 dPa • s) (° C.) Hydrolytic0.0315 0.0310 0.0310 0.0295 0.0290 resistance (ml/g) Linear thermal 54.455.1 53.7 expansion coefficient (from 30° C. to 380° C.) Transmittanceat a wavelength of 450 nm (thickness: 1 mm) (%)

TABLE 2 Mass % No. 12 No. 13 No. 14 No. 15 No. 16 SiO₂ 72.22 72.42 71.4270.42 71.42 Al₂O₃ 5.40 5.40 5.90 6.40 6.15 B₂O₃ 9.50 9.50 10.00 10.509.75 CaO BaO 1.30 1.30 1.30 1.30 1.30 Na₂O 5.50 5.30 5.30 5.30 5.30 K₂O2.35 2.35 2.35 2.35 2.35 Cl 0.08 0.08 0.08 0.08 0.08 Fe₂O₃ 1.15 1.151.15 1.15 1.15 TiO₂ 2.50 2.50 2.50 2.50 2.50 SnO₂ Na₂O + K₂O 7.85 7.657.65 7.65 7.65 CaO + BaO 1.30 1.30 1.30 1.30 1.30 CaO/BaO 0.00 0.00 0.000.00 0.00 10^(2.5) dPa · s (° C.) 1,557 1,567 1,584 1,579 1,592 Workingpoint (10⁴ 1,162 1,168 1,178 1,174 1,180 dPa · s) (° C.) Hydrolytic0.0273 0.0270 0.0270 0.0275 0.0270 resistance (ml/g) Linear thermalexpansion coefficient (from 30° C. to 380° C.) Transmittance at a 8 7wavelength of 450 nm (thickness: 1 mm) (%) Mass % No. 17 No. 18 No. 19No. 20 No. 21 No. 22 SiO₂ 70.42 71.42 70.42 72.42 72.92 72.42 Al₂O₃ 6.905.65 5.90 5.40 5.40 5.40 B₂O₃ 10.00 10.25 11.00 9.50 9.50 9.50 CaO 0.400.10 BaO 1.30 1.30 1.30 0.90 0.80 1.20 Na₂O 5.30 5.30 5.30 5.30 5.305.30 K₂O 2.35 2.35 2.35 2.35 2.35 2.35 Cl 0.08 0.08 0.08 0.08 0.08 0.08Fe₂O₃ 1.15 1.15 1.15 1.15 1.15 1.15 TiO₂ 2.50 2.50 2.50 2.50 2.50 2.50SnO₂ Na₂O + K₂O 7.65 7.65 7.65 7.65 7.65 7.65 CaO + BaO 1.30 1.30 1.301.30 0.80 1.30 CaO/BaO 0.00 0.00 0.00 0.44 0.00 0.08 10^(2.5) dPa · s (°C.) 1,608 Working point (10⁴ 1,193 dPa · s) (° C.) Hydrolytic 0.02650.0281 0.0290 0.0305 0.0265 0.0285 resistance (ml/g) Linear thermalexpansion coefficient (from 30° C. to 380° C.) Transmittance at awavelength of 450 nm (thickness: 1 mm) (%)

TABLE 3 Mass % No. 23 No. 24 No. 25 No. 26 No. 27 No. 28 No. 29 No. 30No. 31 No. 32 No. 33 SiO₂ 72.42 72.92 72.42 72.52 72.42 72.32 72.6272.52 72.42 72.47 72.37 Al₂O₃ 5.40 5.40 5.40 5.40 5.40 5.40 5.40 5.405.40 5.40 5.40 B₂O₃ 9.50 9.50 9.50 9.50 9.50 9.50 9.50 9.50 9.50 9.509.50 CaO 0.20 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 BaO 1.10 1.30 1.301.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 Na₂O 5.30 5.30 5.30 5.30 5.405.50 5.30 5.40 5.50 5.40 5.40 K₂O 2.35 2.35 2.35 2.35 2.35 2.35 2.352.35 2.35 2.35 2.35 Cl 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.080.08 Fe₂O₃ 1.15 1.15 1.15 1.05 1.05 1.05 0.95 0.95 0.95 1.00 1.00 TiO₂2.50 2.00 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.60 SnO₂ Na₂O + K₂O7.65 7.65 7.65 7.65 7.75 7.85 7.65 7.75 7.85 7.75 7.75 CaO + BaO 1.301.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 CaO/BaO 0.18 0.00 0.000.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 10^(2.5) dPa · s (° C.) 1,5881,586 1,574 1,587 Working point (10⁴ 1,174 1,174 1,165 1,173 dPa · s) (°C.) Hydrolytic 0.0290 0.0270 0.0280 0.0290 resistance (ml/g) Linearthermal expansion coefficient (from 30° C. to 380° C.) Transmittance ata 14 11 13 13 14 13 12 wavelength of 450 nm (thickness: 1 mm) (%)

TABLE 4 Mass % No. 34 No. 35 No. 36 No. 37 No. 38 No. 39 SiO₂ 72.2772.32 72.37 72.27 72.17 72.22 Al₂O₃ 5.40 5.40 5.40 5.40 5.40 5.40 B₂O₃9.50 9.50 9.50 9.50 9.50 9.50 CaO 0.10 0.10 0.10 0.10 0.10 0.10 BaO 1.201.20 1.20 1.20 1.20 1.20 Na₂O 5.40 5.40 5.50 5.60 5.70 5.60 K₂o 2.352.35 2.35 2.35 2.35 2.35 Cl 0.08 0.08 0.08 0.08 0.08 0.08 Fe₂O₃ 1.001.00 1.00 1.00 1.00 1.05 TiO₂ 2.70 2.65 2.50 2.50 2.50 2.50 SnO₂ Na₂O +K₂O 7.75 7.75 7.85 7.95 8.05 7.95 CaO + BaO 1.30 1.30 1.30 1.30 1.301.30 CaO/BaO 0.08 0.08 0.08 0.08 0.08 0.08 10^(2.5) dPa · s (° C.) 1,5851,568 1,563 1,569 Working point (10⁴ 1,172 1,161 1,157 1,162 dPa · s) (°C.) Hydrolytic 0.0280 0.0290 0.0300 resistance (ml/g) Linear thermal51.8 52.1 52.6 expansion coefficient (from 30° C. to 380° C.)Transmittance at a 10 10 14 14 14 12 wavelength of 450 nm (thickness: 1mm) (%) Mass % No. 40 No. 41 No. 42 No. 43 No. 44 SiO₂ 72.32 72.12 70.6071.70 70.60 Al₂O₃ 5.40 5.40 5.40 5.60 5.70 B₂O₃ 9.50 9.50 9.50 7.5010.20 CaO 0.10 0.10 0.80 0.50 0.60 BaO 1.20 1.20 1.30 1.90 1.30 Na₂O5.55 5.75 5.80 5.90 5.50 K₂o 2.35 2.35 2.40 1.10 1.40 Cl 0.08 0.08 Fe₂O₃1.00 1.00 0.80 1.20 0.70 TiO₂ 2.50 2.50 2.70 4.20 3.10 SnO₂ 0.08 0.000.20 Na₂O + K₂O 7.90 8.10 8.20 7.00 6.90 CaO + BaO 1.30 1.30 2.10 2.401.90 CaO/BaO 0.08 0.08 0.62 0.26 0.46 10^(2.5) dPa · s (° C.) 1,5731,526 1,575 1,555 Working point (10⁴ 1,166 1,138 1,183 1,142 dPa · s) (°C.) Hydrolytic 0.0295 0.0420 0.0370 0.0350 resistance (ml/g) Linearthermal 51.7 53.0 55.8 51.8 51.6 expansion coefficient (from 30° C. to380° C.) Transmittance at a 18 13 13 wavelength of 450 nm (thickness: 1mm) (%)

TABLE 5 Mass % No. 45 No. 46 No. 47 No. 48 No. 49 No. 50 SiO₂ 69.8770.32 70.62 68.57 69.97 70.37 Al₂O₃ 5.40 5.30 4.90 5.90 5.40 5.40 B₂O₃9.50 9.30 9.00 10.00 9.50 9.50 CaO 0.40 0.40 0.40 0.40 0.40 0.40 BaO1.30 1.25 1.30 1.30 1.30 1.30 Na₂O 5.30 5.20 5.30 5.30 5.30 5.30 K₂O2.35 2.30 2.35 2.35 2.35 2.35 Cl 0.08 0.08 0.08 0.08 0.08 0.08 Fe₂O₃1.20 1.25 1.20 1.25 1.10 1.20 TiO₂ 4.50 4.50 4.75 4.75 4.50 4.00 SnO₂0.10 0.10 0.10 0.10 0.10 0.10 Na₂O + K₂O 7.65 7.50 7.65 7.65 7.65 7.65CaO + BaO 1.70 1.65 1.70 1.70 1.70 1.70 CaO/BaO 0.31 0.32 0.31 0.31 0.310.31 10^(2.5) dPa · s (° C.) Working point (10⁴ dPa · s) (° C.)Hydrolytic resistance (ml/g) Linear thermal expansion coefficient (from30° C. to 380° C.) Transmittance at a 9 8 10 11 13 wavelength of 450 nm(thickness: 1 mm) (%)

The samples were each produced as described below.

First, 500 g of a batch was blended so as to give the composition shownin the table and melted at 1,650° C. for 3.5 hours in a platinumcrucible. The content was stirred twice in the course of melting inorder to reduce bubbles in the sample. After the melting, the resultantglass was rapidly cooled with a roller made of a metal, and wasprocessed into shapes required for measurement and subjected to variousevaluations. The results are shown in the tables. In each of Examplesshown in Tables 1 to 4, the glass was melted so that the ratio of Fe²⁺to iron atoms contained in the glass was 60% or more. In addition, ineach of Examples shown in Table 5, the glass was melted so that theratio of Fe²⁺ to iron atoms contained in the glass was less than 60%.

The working point was measured by a platinum sphere pull up method, andwas determined as a temperature at which the glass had a viscosity of10^(4.0) dPa·s. In addition, the temperature at which the glass had aviscosity of 10^(2.5) dPa·s was determined by the same method.

The hydrolytic resistance test was performed by a method in conformitywith the European Pharmacopoeia 7.0. Detailed test procedures are asdescribed below. The glass sample was crushed in an alumina mortar withan alumina pestle and classified into a particle diameter of from 300 μmto 425 μm with a sieve. The resultant powder was washed with ionexchanged water and acetone and dried in an oven at 140° C. 10 g of thepowder sample after the drying was loaded into a quartz flask, and 50 mLof ion exchanged water was further added thereto and the flask wascovered with a closure. The quartz flask including the sample was placedin an autoclave and subjected to treatment. The treatment conditionswere as follows: a temperature was increased at a rate of 1° C./min from100° C. to 121° C., and was then retained at 121° C. for 30 minutes, andwas reduced at a rate of 0.5° C./min to 100° C. The solution in thequartz flask was transferred to another beaker, the quartz flask wasfurther washed with 15 mL of ion exchanged water three times, and alsothe washing liquid was added to the beaker. A methyl red indicatorsolution was added to the beaker, and the content was titrated with a0.02 mol/L hydrochloric acid solution. The amount of hydrochloric acidconsumed until neutralization was achieved was read, and was convertedto the consumption amount of hydrochloric acid per gram of glass. Theresultant amount was shown in the tables. Even when the powder of theglass sample was washed with distilled water and ethanol instead of ionexchanged water and acetone, the same results are obtained.

The linear thermal expansion coefficient was measured with a dilatometer(NETZSCH DIL 402C) for a glass processed into a column shape measuring20 mm in length by 5 mm in diameter. The linear thermal expansioncoefficient was calculated from an elongation amount of the entirelength of the glass within the temperature range of from 30° C. to 380°C.

The transmittance was measured with a spectrophotometer (SHIMADZUUV-2500) for a glass processed into a thickness of 1 mm and having amirror-finished surface. A measurement wavelength range was set to from200 nm to 800 nm, a slit width was set to 5 nm, a scan speed was set toa medium speed, and a sampling pitch was set to 1 nm. In each of Tables1 to 5, a value for the “transmittance at a wavelength of 450 nm(thickness: 1 mm) (%)” is shown. The wavelength of 450 nm is awavelength at which the highest transmittance value in the wavelengthrange of from 290 nm to 450 nm is obtained.

In the European Pharmacopoeia 7.0, an upper limit of the transmittanceat a wavelength of from 290 nm to 450 nm is specified. The upper limitis set depending on the volume of a container. Containers each having avolume of from 2 mL to 20 mL may be processed from the glass having athickness of 1 mm. In the case of the containers each having a volumewithin the above-mentioned range, the corresponding upper limits of thetransmittance are as follows: 15% or less in the case of a volume offrom 2 mL to 5 mL; 13% or less in the case of a volume of from 5 mL to10 mL; and 12% or less in the case of a volume of from 10 mL to 20 mL.

The glass for a pharmaceutical container of the present inventionmanufactured under the above-mentioned conditions satisfied at least oneof the upper limits of the transmittance at a wavelength of from 290 nmto 450 nm specified in the European Pharmacopoeia 7.0.

In addition, Sample Nos. 42 to 44 serving as Comparative Examples eachhad a high value for CaO+BaO and/or a high value for CaO/BaO, and hencehad poor hydrolytic resistance.

INDUSTRIAL APPLICABILITY

The glass for a pharmaceutical container of the present invention issuitable as a glass for manufacturing a pharmaceutical container, suchas an ampoule, a vial, a pre-filled syringe, or a cartridge.

Further, the glass for a container of the present invention is excellentin light shielding properties, and hence a content thereof is lessliable to be altered through irradiation with light, and the glass isexcellent in function of blocking ultraviolet light. In addition, theglass for a container of the present invention is excellent inhydrolytic resistance. Therefore, the glass for a container of thepresent invention is particularly suitable for the case in which thecontent thereof is to be protected from deterioration. For example, theglass for a container of the present invention may be suitably used forbiotechnology applications, experimental instruments, such as a Petridish and a beaker, a bottle for cosmetics, a bottle for beverages, afood container, or the like.

The invention claimed is:
 1. A glass for a pharmaceutical container, which comprises as a glass composition, in terms of mass %, 67% to 81% of SiO₂, more than 4% to 7% of Al₂O₃, 7% to 14% of B₂O₃, 6% to 8.55% of Na₂O+K₂O, 0.8% to 1.8% of CaO+BaO, 0.1% to 1.8% of BaO, 0.5% to less than 2% of Fe₂O₃, and 1% to 5% of TiO₂, and satisfies a relationship of CaO/BaO≤0.4, wherein the glass has a transmittance at a wavelength of 450 nm that is 15% or less when having a thickness of 1 mm.
 2. The glass for a pharmaceutical container according to claim 1, wherein the glass comprises as a glass composition, in terms of mass %, 70% to 78% of SiO₂, 5% to 7% of Al₂O₃, 8% to 11% of B₂O₃, 6% to 8.55% of Na₂O+K₂O, 0.8% to 1.8% of CaO+BaO, 0.8% to 1.2% of Fe₂O₃, and 2% to 5% of TiO₂, and satisfies a relationship of CaO/BaO≤0.3.
 3. The glass for a pharmaceutical container according to claim 2, wherein the glass comprises as a glass composition, in terms of mass %, 9% to 11% of B2O₃.
 4. The glass for a pharmaceutical container according to claim 1, wherein the glass comprises as a glass composition, in terms of mass %, 9% to 11% of B₂O₃.
 5. The glass for a pharmaceutical container according to claim 1, wherein the glass has a consumption amount of 0.02 mol/L hydrochloric acid per unit glass mass 0.035 mL or less in a hydrolytic resistance test by a glass grains test method in conformity with the European Pharmacopoeia 7.0.
 6. The glass for a pharmaceutical container according to claim 1, wherein the glass has a working point of 1,200° C. or less.
 7. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container of claim
 1. 8. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container of claim
 2. 9. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container of claim
 4. 10. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container of claim
 5. 11. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container of claim
 6. 12. A glass tube for a pharmaceutical container, comprising the glass for a pharmaceutical container of claim
 3. 13. A glass for a container, which comprises as a glass composition, in terms of mass %, 67% to 81% of SiO₂, more than 4% to 7% of Al₂O₃, 7% to 14% of B₂O₃, 6% to 8.55% of Na₂O+K₂O, 0.8% to 1.8% of CaO+BaO, 0.1% to 1.8% of BaO, 0.5% to less than 2% of Fe₂O₃, and 1% to 5% of TiO₂, and satisfies a relationship of CaO/BaO≤0.4, wherein the glass has a transmittance at a wavelength of 450 nm that is 15% or less when having a thickness of 1 mm.
 14. A glass tube for a container, comprising the glass for a container of claim
 13. 